Detergent composition



July 25, 1967 cow ET AL 3,332,874

DETERGENT COMPOSITION Filed Dec. 25, 1965 2o--- G DETERGENT A o gg 2 o DETERGENT B" o RATIO BY WEIGHT OF DETERGENT A To DETERGENT B *cnAGs Todd L.Cowc|rd Curl Barker INVENTORS ATTORNEYS v United States Patent 3,332,874 DETERGENT COMPOSITION Todd L. Coward and Carl Barker, Cincinnati, Ohio, as-

signors to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio Filed Dec. 23, 1965, Ser. No. 515,826 13 Claims. (Cl. 252-137) This invention relates to a novel detergent compositron. It also relates to a detergent composition which embodies a synergistic mixture of surface active compounds.

The compositions described herein are useful for both light-duty and heavy-duty applications. They have special usefulness, however, in connection with detergent com-positions designed for light-duty cleaning situations. The terms light-duty and heavy-duty as applied to detergency have acquired fairly definite meanings in the art. The term light-duty is used in the description of this invention in its usually accepted context, i.e., namely, as a semi-specialty product designed for dish-washing and laundering fine fabrics by hand. The term is also used to difierentiate between this class of products and the heavy-duty laundering products used in standard and automatic washing machines which depend substantially for their satisfactory performance on the use of large amounts of various types of additives such as suds boosters, detergency' builders, sequestering agents and other similar functional ingredients.

Light-duty applications include the hand washing of dishes and lightly soiled fine fabrics which fabrics cannot as a rule withstand the vigorous treatment of machine laundering. Also, light-duty washing situations are those which generally call for a gentle washing action in cool or lukewarm water. It is well known by those skilled in the art that compositions designed for such uses must have certain performance properties which distinguish them from heavy-duty cleaning composition-s. For instance, they must be mild to the skin, possess high sudsing properties, and also possess cleaning power in water sol1't(1)1(1)0n; having cool or lukewarm temperatures, e.g. below -On the other hand, heavy-duty applications are those cleaning situations which involve heavily soiled fabrics and clothing. One of the considerations involved in such cleaning processes is the use of vigorous mechanical action usually in hot water having temperatures between about 120 F. up to about 200 F. The problems presented by high soil loads on fabrics such as cotton are unlike those dealt with in light-duty situations. Thus the different cleaning situations require the use of specially formulated detergent compositions.

. In addition to the desirable properties mentioned above inconnection with light duty uses, a detergent compo- SllIlOIhShOuld serve as a wetting agent to solubilize and emulsify greasy soils and help remove them from soiled articles, especially from dishes. The composition should be able'to disperse and suspend soil once it is removed from the articles being washed so that the soil does not redeposit on the articles. A light-duty dishwashing compos tion moreover, should be able to provide quickly a copious amount of stable suds that will form a long lasting suds layer over the washing solution. The blanket of suds produced should be so stable that it will last throughout the entire washing operation. The cleaning capability of a dishwashing solution is frequently gauged by the amount of suds present during the washing process. In addition, the detergent composition should perform these functions efficiently over the wide range of washing conditions normally encountered in dishwashing and fine fabric laundering processes (water temperature, wa-

3,332,874 Patented July 25, 1967 ter hardness, soil type, soil load, etc.). Special caution must be taken to insure that a dishwing composition will be mild on the skin. Still further, it is desirable that a detergent composition when formulated into a liquid product should provide a physically stable system over a wide range of storage conditions. Economic consideration-s also play an import-ant role in the preparation of these types of compositions.

It is a primary object of the present invention to provide a detergent composition preferably a liquid formulation which performs satisfactorily in all or most of the foregoing areas, and which excels in some of them, especially sudsing. Thus, it is an object of this invention to provide a liquid detergent composition which ofiers synergistic sudsing performance characteristics which make it especially valuable for dishwashing and fine fabric laundering. It is another object to provide a light-duty liquid composition which consists essentially of an aqueous vehicle and a synergistic mixture of the hereinafter described active detergent compounds. These and other objects of the present invention will become apparent from the following description.

FIGURE 1 is a drawing of a graph presenting data showing the surprising synergistic sudsing results made possible by the detergent compositions of the present invention.

All percentages and ratios given hereinafter are by weight unless otherwise specified.

It has now been discovered that a detergent composition having superior sudsing performance characteristics can be prepared which consists essentially of a synergistic mixture of Detergent A and Detergent B wherein Detergent A is an ingredient which comprises from about 30% to about 70% of Component A, from about 20% to about 70% of Component B and from about 2% to about 15% of Component C, wherein:

(a) Said Component A is a mixture of double-bond positional isomers of water-soluble salts of alke-ne-l-sulfonic acids containing from about 12 to about 16 carbon atoms, said mixture of positional isomers including by weight about 10% to about 25% of an alpha-beta unsaturated isomer, about 30% to about 70% of a betagamma unsaturated isomer, about 5% to about 25% of a gamma-delta unsaturated isomer, and about 5% to about 10% of a delta-epsilon unsaturated isomer;

(b) Said Component B is a mixture of water-soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds containing from about 12 to about 16 carbon atoms, the functional units being hydroxy and sulfonate radicals with the sulfonate radical always being on the terminal carbon and the hydroxyl radical being attache-d to a carbon atom at least two carbon atoms removed from the terminal carbon atom; and (c) Said Component C is a mixture comprising from 30-95% water-soluble salts of alkene disulfonates containing from about 12 to about 16 carbon atoms, and from about 5% to about 70% water-soluble salts of hydroxy disulfonates containing from about 12 to about 16 carbon atoms, said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atom, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate radical attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group; and wherein Detergent B is an alkyl glyceryl ether sulfonate having a straight chain alkyl group having from about to about 16 carbon atoms, the cation of said sulfonate being selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, ammonium, sodium, and potassium cations and mixtures thereof.

According to the present invention the synergistic sudsing results are obtained when Detergent A and Detergent B are present in admixture at a ratio of Detergent A to Detergent B of from about 10:1 to about 1:7, by weight. Outstanding results are obtained within a narrower preferred ratio of Detergent A to Detergent B of 6:1 to 1:4, by Weight. The amount of suds produced and the stability thereof drops off markedly when the 10:1 and 1:7 by weight ratios are exceeded. Within this range and especially within the preferred range, the benefits of synergism are best obtained.

According to the present invention, Detergent A is itself a mixture of certain compounds. As noted above it is basically a mixture of three components each of which has a specific composition. A detailed discussion of the makeup of Detergent A is presented below.

A preferred percentage range by weight for Component A is from about 35% to about 65%, for Component B it is from about 25% to about 60%, and for Component C it is from about 3% to about 12%. Component A is comprised essentially of the prescribed ranges of the following compounds.

In the preceding formulas x is an integer in the range from about 6 to about 10, preferably about 8 to 10, and M represents any cation that forms a water-soluble salt such as alkali metals, e.g. sodium and potassium, and ammonium, and substituted ammonium compounds, e.g. trialkylammonium and trialkylolammonium compounds. Specific examples of substituted ammonium compounds are triethylammonium, triethylamm-onium, and triethanolammonium. Others will be apparent to those skilled in the art. The symbols x and M have the same meaning throughout the description of the present invention. There can also be present, minor amounts of other double-bond positional isomers. This is the case, for example, when the composition is prepared by the sulfonation of alpha olefins with uncomplexed sulfur trioxide. Such minor amounts, i.e. less than 10% by weight, do not materially alter the excellent detergent properties of the composition.

Whereas, Component A is a blend or mixture of certain unsaturated isomeric aliphatic compounds, Component B consists of a mixture of certain saturated aliphatic corn-pounds. A minor amount of unsaturation can be included in this mixture but preponderantly the compounds are saturated. The bifunctionality of these alkane compounds is due to the presence of a hydroxyl group and a sulfonate radical on the same molecule. It has been discovered that the sulfonate radical must be located on the terminal carbon atom. It also has been discovered that the situs' of the hydroxyl group is an especially important factor in the compounds that can comprise Component B. For example, if the hydroxyl group and the sulfonate radical are attached to adjacent carbon atoms, the valuable detergent properties of the Component B compounds are substantially decreased. This is especially true when the alpha and beta carbons are the two sites of attachment. The critical structural arrangement which must exist in order for the compounds to be detergents is that the sulfonate radical must be in the alpha position and the hydroxyl radical must be attached to a carbon atom at least two carbons removed, for example, to the third, fourth or fifth carbons, i.e. on the gamma, delta, or epsilon carbons. In other words, the carbon to which the hydroxyl group is attached should be separated from the carbon bearing the sulfonate radical by at least one methylene group along the aliphatic chain.

Thus, Component B consists of a mixture of the following bifunctionally-substituted saturated aliphatic compounds.

The value of x and M are as previously set forth.

Component B can also include minor quantities, for example, less than about 10% of compounds wherein the hydroxyl group is attached elsewhere along the carbon chain, e.g. on the sixth carbon atom, without materially altering the overall detergent properties of the compositions. The 3-, 4-, and 5-hydroxy n-alkyl sulfonate compounds, illustrated above, are preferred ingredients in Component B and at least of the hydroxy radical substitution must be in the 3, 4, and 5 positions.

In this same connection, it has also been noted that corresponding beta-hydroxy n-alkyl sulfonate compounds are relatively poor detergent compounds. Not only are they comparatively poor detergent, but it has been discovered also that such compounds constitute an actual load on the present detergency system. For this reason, the level of such compounds should be held to a minimum. It is noted though, that minor amounts of betahydroxy n-alkyl sulfonate compounds can be tolerated in the synergistic compositions of this invention provided that Components A, B, and C of Detergent A otherwise contain the essential ingredients herein described in the proportions and percentages specified.

The alkene disulfonates should preferably comprise from about 40% to about 80% of the highly polar polyfunctionally substituted aliphatic compounds which make up Component C. These alkene disulfonates should preferably contain from about 12 to about 16 carbon atoms. As mentioned above, one sulfonate group is attached to the terminal carbon atom. The second sulfonate group is attached to an internal carbon atom that is not more than about six carbon atoms removed from the terminal carbon. In other words, the second sulfonate functional group can be attached to the second through about the seventh carbon atom. Component C can also include minor amounts of compounds in which the second sulfonate is located more internally than the seventh carbon, such as, for example, on the eighth carbon, etc. There is no apparent advantage in having these latter compounds present in the composition, however. According to a preferred embodiment, the major portion, that is from about 60% to about of the alkene disulfonates, should be 1,2 and 1,3 disulfonates.

The alkene double bond can be distributed between the terminal carbon and about the seventh carbon atom; such unsaturation includes, for instance, alpha-beta, betagamma, gamma-delta, delta epsilon, epsilon-zeta, and zeta-eta unsaturation. Preferably, the double bond should be distributed between the second to the sixth carbon atom. It should be noted that the alkene double bond can be even more internally located than between the zeta-eta carbons, but again no apparent advantage is gained thereby.

Thus, it can be seen that the alkene disulfonates of Component C contain the polyfunctional combination of a double bond and two sulfonate groups in an important structural relationship. The preferred compounds as ingredients of the alkene disulfonate portion of Component C are 2-alkene-1,2-disulfonate; 3-alkene-1,2-disulfonate; and 4-alkene-1,2-disulfonate of the 1,2 disulfonate species; and 3-alkene-1,3-disulfonate; 4-alkene-1,3-disulfonate; and 5-alkene-1,3-disulfonate of the 1,3 disulfonate species. The alkene group can contain from about 12 to about 16 carbon atoms and preferably about 14 to 16 carbon atoms. The sodium and potassium salts of these compounds are preferred.

Examples of alkene disulfonate compounds are the following in which a carbon chain length of 16 was selected as being representative, having sulfonate attachment sites of 1,2 and 1,3;

As mentioned above, Component C contains the aforementioned and illustrated alkene disulfonates. It also contains from about 5% to about 70%, and preferably about 20% to about 60%, water-soluble salts of hydroxy disulfonates containing from about 12m about 16 carbon atoms. The terminal carbon atom has attached to it one of the sulfonate groups. The second sulfonate group can be attached to an internal carbon atom not more than about six carbon atoms removed fromsaid terminal carbon atom. The required hydroxy group is attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group.

The preferred sites of attachment for the hydroxy group on the 1,2 disulfonate species are the fourth and fifth carbon atoms to yield 4-hydroxyalkane-1,2-disulfonates and S-hydroxyalkane-1,2-disulfonates. For the 1,3- disulfonates the preferred sites of attachment for the hydroxy group are the fifth and the sixth carbon atoms to yield S-hydroxyalkane-1,3-disulfonates and 6-hydroxyalkane-1,3-disu1fonates. The alkane hydrocarbons as before are those having 12 to 16 carbon atoms and preferably about 14 to 16 carbon atoms. According to a preferred embodiment, the major portion, that is, from about 60% to about 95% of the hydroxy disulfonates should be 1,2 and 1,3 disulfonates.

Thus, for example, the following compounds are contemplated. Again, a 16 carbon 1,2 and 1,3 disulfonate compound is presented as being representative.

It is postulated that a second polar group, as in Components B and C, spaced a critical distance from a terminally attached polar group in a detergent molecule modifies the crystalline latice structure in such a way as to improve markedly the solubility characteristics of the compound. While this is not known for certain, it is offered as one possible explanation for the exceptional detergent properties of the compositions of the present invention.

Detergent A as described herein can be prepared in any suitable manner so long as the above teachings are adhered to. For instance, each of the ingredients can be synthesized separately and then mixed according to the stated proportions. On the other hand, it is possible to prepare the compositions of the present invention according to a novel process describedin copending patent application Ser. No. 423,292 filed J an. 4, 1965, by Adriaan Kessler and Phillip F. Pfiaumer, and another patent application being filed concurrently herewith.

If it is desired to synthesize separately the individual components of Detergent A, it is possible to do so according to the procedures in the following discussion. Any other suitable methods can be used. The symbol R as used in the following equation represents an aliphatic hydrocarbon radical that would allow for a total of carbon atoms in the molecule between about 12 and about 16. The alpha-beta unsaturated sulfonate containing aliphatic compounds of Component A can be prepared readily by dehydrochlorinating a 2-chlorosulfonic acid derivative. A fairly detailed discussion of a suitable preparative route appears in an article in the Journal of Organic Chemistry, vol. 1949, page 46, written by J. D. Rose and A. Lambert. The starting step for this synthesis is a reaction between a long chain epoxide and sodium bisulfite to produce a 2-hydroxy-1-sulfonate derivative of the particular long chain epoxide used. This reaction product is condensed with PCl to prepare the aforementioned 2-chlorosulfonic acid derivative which in turn is reacted with sodium carbonate to yield an alpha-beta unsaturated compound.

The other preferred double-bond positional isomers of Component A, i.e., the beta-gamma, gamma-delta, and delta-epsilon can be prepared by the thermal dehydration of hydroxy-sulfonates. According to the following reaction, the thermal dehydration of the sodium salt of 7 3-hydroxy-sulfonate results in the preparation of a reaction mixture containing the beta-gamma isomer and the gamma-delta isomer.

RCHzCH=CHCH2SOaNa ROH=CHCH2CH2SO3N21 Similarly a reaction mixture of a gamma-delta and a delta-epsilon double-bond isomer compound can be prepared by using a 4-hydroxysulfonate as a starting material:

The foregoing synthesis of the double-bond positional isomers follows closely the well known dehydration of an organic alcohol as is mentioned in such standard texts as Whitmores Organic Chemistry, second edition, pages 39-41.

There is no need to separate the reaction product of the two illustrated dehydration reactions. The reaction product can be formulated directly into a detergent composition according to the present invention. If, for some reason, it is desired to work with pure ingredients, they can be separated into pure forms.

The hydroxy sulfonates of Component B, such as the preferred 3-, 4-, and 5-hydroxy compounds can be prepared by the free radical addition of sodium bisulfite to the corresponding 3-, 4-, or 5-hydroxy-l-olefin, respectively:

Free Radical sodium 3-hydr0xyalkane sulfonate RCH(OH) CHzCHzSOsNa sodium 4-hydroxyalkane sulfonate aldehyde Grignard 4-hydroxy-1-olefin Reagent A discussion of the conversion of hydroxyolefins produced by preceding Equations a and b to hydroxy sulfonates appears in an article written by J. Willens, Bulletin of the Chemical Society of Belgium, vol. 64, page 427 (1955).

It is to be understood that other hydroxy sulfonates as desired can be prepared by using different Grignard reagents in the reaction equation set forth above.

The alkene disulfonates and the hydroxy disulfonates which comprise Component C may also be prepared separately by any known manner. For instance, the -hydroxy disulfonates may be prepared by epoxidizing olefin sulfonic acid isomers, and then opening the epoxide ring with sodium bisu-lfite by standard reaction techniques. The hydroxy disulfonates may then be dehydrated by reactions known to those skilled in the art to yield the corresponding isomeric alkene disulfonates.

As mentioned earlier, the Detergent A components should contain from about 12 to about 16 carbon atoms. It is preferred, however, to have the compounds contain from 14 to 16 carbon atoms. It is not necessary that each of the compounds contain the same number of carbon atoms. Mixtures of different chain lengths within the prescribed ranges can be used.

The following compositions are illustrative of the make up of Detergent A according to the present invention wherein the percentages are by weight and wherein Components A, B and C total up to of Detergent A. The percentages listed for each ingredient are by weight of that particular ingredient in Detergent A.

Detergent A can be comprised as follows with a chain length of 16 carbons being representative:

CH CH SO Na .5 C H CH=CHCH CH(SO Na) CH CH SO Na .5 C H CH(OH) CH CH(SO Na) CH SO Na 1.5 C H CH(OH)CH CH CH(SO Na) CH SO Na 1.5

C H CH (OH) CH CH(SO CHg-CHg-SO3N3.

C10H21 CH(OH) CH CH SO Na .5

Total Component C 10 This Detergent A composition listed above has excellent detergent and synergistic sudsing properties when mixed with Detergent B according to the proportions described herein.

Another illustrative example of Detergent A is as follows:

Component A: Percent C14H2QCHZCHSO3NH. 9 C H CH=CHCH SO Na C H CH=CHCH CH SO Na C H CH=CHCH CH CH SO Na 10 Total Component A 65 Component B: Percent C13H2'7CH(OH) CH2CH2SO3N3. C12H25CH(OH) CH CH CH SO Na C H CH(OH)CH CH CH CH SO Na 3 Total Component B 23 9 Component C: Percent C1oH2 -CH2 CH (SO Na) 1 C1OH2I-CH2-CHZCH=CH"-CH CH SO Na 3 5 C H CH CH:CHCH

CH2CH2SO3Na .5 C H -CH CH CH CH(SO NH.)

CH=CHSO Na .5 C H -CH CHCH SO Na .5 C H -CH CH CH(OH) CH CH (SO Nfl) -CH SO Na 3.0 CIOH21CHZ-CH -'CH2 CH2 CH(SO Na) CH SO Na 1.0 C H CH CH(OH) CH CH(SO Na)*CH -CH SO Na 1.0

Total Component C 12 This detergent A composition also offers excellent detergent properties of cleaning and synergistic sudsing in admixture with Detergent B as described herein.

Detergent B as described above is a =monoethanolamine, diethanolamine, triethanolamine, sodium potassium or ammonium alkyl glyceryl ether sulfonate in which the alkyl group is a straight chain alkyl group having from about 10 to about 16 carbon atoms. In one preferred embodiment of the present invention the alkyl group is derived from coconut alcohol and especially the middlecut coconut alcohol containing 2% C 66% C 23% C and 9% C This preferred compound is, at times, referred to hereinafter as CnAGS. A preferred range for the carbon chain length is 12 to 16 carbon atoms.

Specific examples mentioned by way of illustration only are sodium dodecyl glyoeryl ether sulfonate, sodium tetradecyl glyceryl ether sulfonate, sodium hexadecyl glyceryl ether sulfonate. Mixtures of such compounds having different chain lengths can be used and in such mixtures those are preferred in which alkyl groups in the mixture contain 12 carbon atoms. This is the situation for example when coconut oil derived alkyl groups are used. Other mixtures can also be used with very satisfactory results.

Other examples of alkyl glyceryl ether sulfonates useful in the present invention and methods for their preparation are described in US. Patent 3,024,273 issued to D. D. Whyte et al. and dated March 6, 1962.

The synergistically improved sudsing performance of the novel compositions of the present invention was discovered by preparing light-duty liquid compositions containing different detergent compounds as sole cleaning agents and also representative mixtures of such detergent compounds. The compositions were standardized to include a total of 30% by weight of an active deter-gent ingredient with the balance, 70%, being an aqueous vehicle.

Detergent A and Detergent B were each first tested separately and then in certain prescribed mixtures. Thus, for example, a composition was prepared consisting of 30% of just Detergent A and 70% water. Another composition was prepared consisting of 30% of just Detergent B and 70% water. Then mixed compositions were prepared consisting of 25% Detergent A and 5% Detergent B, and 15% Detergent A and 15% Detergent B.

The detergent referred to as Detergent A in FIGURE 1 and used for calculating the essential proportions shown there was a mixture of 30% C compounds, 40% C 4, compounds, and 30% C compounds as described in detail above. More specifically Detergent A had essentially the following composition. Approximately 65% of the C compounds consisted of a mixture of sodium salts of alkene-l sulfonic acids in which the double bond was distributed between the first and fifth carbon atom; approximately 35% of the C compounds consisted of a mixture of sodium salts of bifunctionally substituted saturated aliphatic compounds having a sulfonate group terminally attached and hydroxyl radical attached to the third, fourth or fifth carbon atom; and approximately 10% of the C compounds consisted of mixture of (1) sodium salts of alkene disulfonates having a terminally attached sulfonate group and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from the terminal carbon atom, and the double bond being distributed between the terminal carbon atom and the seventh carbon atom, and (2) sodium aliphatic hydroxy disulfonate compounds having a terminal sulfonate group, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from the terminal carbon atom, and a hyd-roxy group attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group. The C compounds and the C compounds consisted of the same distribution of compounds as just recited for the C compounds.

Detergent B was the sodium salt of middle-cut coconut alkyl glyoeral ether sulfonate containing 2% C10, 66% C 23% C and 9% C It is referred to as CnAGS.

The specific testing procedure designed to evaluate these several detergent compositions under simulated home performance situations is described. A dishpan was prepared containing one gallon of water with a hardness of 7 grains, a temperature of F. and a pH of 7. To this was added in separate tests 7.25 cc. of each of the detergent compositions being tested. The wash-ing solution containing the detergent composition was mechanically agitated to produce the maximum suds level which was measured. This is referred to as the original suds level. Agitation was by means of a mechanical stirrer.

After this original suds level was obtained, a series of five ordinary dinner plates each soiled with about 2 grams of standardized fatty soil (a triglyceride shortening) were washed in the prepared test solution. The suds height was again measured. This procedure was repeated a fixed number of times with a suds height measurement being taken after each set of five dishes were washed. An average was then calculated for the several sud-s height measurements, and the average was then expressed in terms of a percentage of the original suds height. This percentage figures is regarded as a relative measure of two extremely important areas of dishwashing and fine laundry performance, namely, initial suds volume and even more importantly, suds stability in the presence of increasing soil load. The results are highly dependable and reproducible. Those skilled in performing this evaluation known from experience that a difference in suds height of from about 3% to about 5% is considered significant.

The results of these evaluations are presented in FIG- URE 1.

Referring to FIGURE 1, it can be seen that the average values obtained for Detergent A and Detergent B when each was used as the sole detergent are markedly lower than for mixtures of these two detergent compounds. It should be emphasized that the demonstrated synergistic sudsing performance was totally unexpected. There is no known criteria by which it is possible to predict this type of behavior. It can be seen from FIGURE 1 that an equal weight mixture or a 1:1 mixture by parts or by weight resulted in an average percent suds during washing of 43%. This can be compared with an average percent of only 34% for Detergent A alone and 36% for Detergent B alone. A 5:1 ratio (see 25:5 figure in FIG- URE 1) gave an ave-rage percentage of 39%.

In regard to these performance results as tubulated in FIGURE 1, it should :be appreciated that they are more relevant to show relative sudsing results than to establish absolute comparisons. When other representative compounds are used from the herein disclosed classes of Detergent A and Detergent B, the results may not coincide exactly with the graph line of FIGURE 1. There may be a deviation of the curve depending, for example, on the chain length of the alkyl groups or the specific cation of the sulfonate group. In all events, however, the synergistic sudsing results described herein which form the principal basis for the present invention are obtained with mixtures prepared according to proportions described above.

According to the present invention, the syntergistic detergent mixtures of the present invention consisting of the critically proportioned ingredients can be prepared readily into liquid detergent compositions. The essential ingredients for such compositions are the novel synergistic mixture and a liquid vehicle therefor. When used in such a manner the detergent composition can consist of from about 5% to about 50% of the detergent mixture and the balance of 50%95% being water. Preferably, however, the detergent synergistic mixtures can range from about to about 35% by weight of the composition with the remaining 65%90% being water.

Moreover, the detergent mixtures of the present invention can be used with other materials to form complete detergent formulations. Such complete compositions can contain the detergent mixtures of this invention in admixture, for example, with water soluble inorganic alkaline builder salts, organic sequestering agents, or mixtures thereof, hydrotropes, solubilizing agents, antitarnishing agents and water.

The builders and sequestrants can be employed at levels of from about 4% to about 30% by weight of the composition and preferably from about 8% to Water soluble inorganic alkaline builder salts which can be used alone or in admixture are alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. Specific examples of such salts are sodium and potassium, tripolyphosphate, sodium and potassium carbonate, sodium and potassium tetraborate, sodium and potassium pyrophosphate, sodium bicarbonate, sodium hexametaphosphate, sodium sesquicarbonate, sodium mono and 'diortho phosphate and potassium bicarbonate. Such inorganic builder salts enhance the overall cleaning characteristic of the novel synergistic mixtures of the present invention. Generally the potassium salts of these compounds are preferred for reasons of solubility. Potassium pyrophosphate is the single preferred builder. for use in the present invention.

Examples of organic alkaline builder salts which can be used alone or in admixture are alkali metal, ammonium or substituted ammonium, aminopolycarboxylates, e.g., sodium and potassium N-(Z-hydroxyethyl)-ethylenediaminetriacetates, sodium and potassium nitrilotn'acetates and sodium, potassium and triethanolarnmonium- N-(2-hydroxyethyl)-nit-rilodiacetates. Mixed salts of these polycarboxylates are also suitable. Other valuable polycarboxylate builder compounds are the sodium and potassium salts of polymaleate, polyitaconate, and polyacrylate. The alkali metal salts of phytic acid, e.g., sodium phytate, are also suitable as organic alkaline builder salts (see U.S. Patent 2,739,942).

Polyphosphonates are also valuable builders in terms of the present invention including specifically sodium and potassium salts of ethane-l-hydroxy-l, l-diphosphonate, sodium and potassium salts of methylene diphosphonate, sodium and potassium salts of ethylene diphosphonate, and sodium and potassium salts of ethane-1,1,2-triphosphonate. Other examples include the alkali metal salts of ethane-Z-carboxy-l,l-diphosphonic acid, hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane-l-hydroxy-l,1,2-triphosphonic acid, ethane-Z-hydroxy-l,1,2-triphosphonic acid, propane 1,1,3,3 tetraphosphonic acid, propane-l,1,2,3-tetraphosphonic acid, and propane-l,2,2,3-tetraphosphonic acid.

Hydrotropes can be added if desired to increase the compatibility of the ingredients of the formulations of this invention. Preferred hydrotrope anions are benzene sulfonate, xylene sulfonate, and toluene sulfonate. They are preferably used as their soluble salts such as: ethanolammonium, diethanolammonium, and triethanolammonium, and especially as the alkali metal, potassium, or sodium salts. Sodium or potassium toluene sulfonate is especially preferred. The hydrotrope is added at levels of from about 0% to about 10% by weight of the composition. Levels of from about 2% to 8% are preferred. The upper limit of about 10% is set by increasing dilution of the product by an ingredient substantially inert so far as sudsing and detergency are concerned. The lower limit is the amount required to achieve a homogeneous solution. It will be appreciated that it is necessary that the formulations of this invention should be liquid at somewhat higher and at somewhat lower temperatures than usual room temperature. The amount of hydrotrope salt used is preferably the minimum amount which will hold the ingredients in solution at the temperature to which it is desired that the formula can be cooled without phase separation.

Solubilizing agents also can be added, if necessary, and those preferred are lower alcohols such as methyl, ethyl and propyl alcohols. They are generally employed at a level of from about 0% to about 25% by weight of the composition and preferably between about 5% to 15% by weight.

As hereinbefore mentioned, various minor ingredients can also be added to the compositions of the present invention. Such normal and desirable additives include perfumes, viscosity central agents, opacifiers, and pigments. In addition, inert materials such as water soluble inorganic salts can also be present in minor amounts, generally as impurities from the various ingredients or as opacifier stabilizers. For example, ethylene glycol distearate or polysytrene can be used as opacifiers in amounts of up to 3% by weight of the composition.

The following compositions are given to Table I by way of examples only and are not intended to limit the scope of the present invention.

Excellent performing light-duty compositions can be prepared having by weight ratios given in Table I in the active detergent ingredient. The compositions prepared accordingly, rapidly produce a synergistically high level of suds volume which is stable over a prolonged period. These compositions are especially useful for dishwashing and the laundering of fine and delicate fabrics as well as the washing of woolens, i.e. sweaters, carpets, etc., where copious amounts of stable suds are desirable.

The following examples represent light-duty detergent compositions which can be prepared according to the present invention. Each provides the valuable synergistic results which are described above in cold or hot water.

The Detergent A represented in the following examples as Detergent A containing 12 Carbon Atoms has the following composition.

(SO Na) 1.0

Total Component C 103 13 The Detergent A represented in the following examples as Detergent A Containing 14 Carbon Atoms has the following composition.

Component A: Percent CIZHZCHZCHSO3NG. C H CH=CHCH SO Na C H CH CHCl-l cH sO Na C H CH=CHCH CH CH SO Na 6 Total Component A 65 Component B: Percent C H CH (OH) CH CH SO Na 20 C H CH(OH)CH CH CH SO Na 5 Total Component B 25 Component C: Percent C H CH=CHCH(SO Na)CH (SO Na) 4.5

20.0% Detergent A containing 14 carbon atoms 10.0% Sodium dodecyl glyceryl ether sulfonate 8.0% Trisodium-ethane-l-hydroxy-l,l-diphosphonate 2.0% Ethyl alcohol 60.0% Water.

Example 20 8.0% Detergent A containing 16 carbon atoms 17.0% Sodium tetradecyl glyceryl ether sulfonate 8.0% Tripotassium salt of nitrilotriacetate 67.0% Water.

Example 21 f 1 0 12.0% Detergent A consisting of one part C and one 2 2( 3 a) part C compounds 3.0% Ammonium coconut alkyl glyceryl ether sulfonate Total Component C ""7 25 6.0% Potassium pyrophosphate The Detergent A represented in the following examples Tripotassillm Salt of y yp as Detergent A Containing 16 Carbon Atoms has the P1101!ate following composition. 50% Ethyl alcohol 68.0% Water. Component A: Pfi Example 22 C 4H CH CHSO3Na c zc c so 33 25.0% Detergent A consisting of 1 part C compounds, 4 3 c =c c c s0 N 13 parts 4 compounds, and 1 P C16 Compounds C11H23CH=CHCH2CH2CH2SO3Na 6 35 5.0% Sodium hexadecyl glyceryl ether sulfonate 30.0% Tetrapotassium pyrophosphate Total ComponentA 65 Watercomponent 13: Percent Each of the preceding compositions can perform excep- C13H27CH(OH)CH2CH2SO3Na 20 tionally well as light-duty liquid detergent compositions. C12H25CH(OH)cHzcHzcHzsoaNa 5 They find special application as dishwashing detergent compositions. All percentages and ratios herein are by Total Component B 25 Weighti While emphasis has been placed in the foregoing de- Component C: Percent scription of the present invention upon detergent formula- 12 25 3 2( 3 tion in liquid form, the compositions herein can also be C H CH=CHCH(SO Na)CH CH (SO Na) 1.5 prepared in solid formulations such as granules, flakes, C H CH(OH)CH CH(SO Na)CH (SO Na) 3.0 powders and other solid particulate forms. Such solid C H CH(OH)CH CH(SO Na) formulations can also contain the synergistic combination CH CH (SO Na) 1.0 of the herein-described detergent compounds in admixture with the builders also described herein ranging from Total Component C 10.0 lightly built compositions to heavily built detergent com- TABLE I Examples DETERGENT A Detergent A Containing 12 Carbon Atoms Detergent A Containing 14 Carbon Atoms Detergent A Containing 16 Carbon Atoms Detergent A Containing a mixture of 10 parts C12,

parts C14, and 10 parts Cm DETERGENT B Sodium coconut alkyl glyceryl ether sulfonate Potassium dodecyl glyceryl ether sulfonate Sodium tetradecyl glyceryl ether sulfonate Ammonium ooconut aklyl glyceryl ether sulfonate. Sodium hexadeeyl glyceryl ether sulfonate -Weight Ratio of Detergent A to Detergent B in in Detergent Composition 3:1 10:1 1:3 2:1 1:1 1:2 5:1 1:5:1 1:4 4:1 5:1 1:5 2:1 1:2 1:1 1:1 6:1

Percent Total Detergent in Composition, Balance being Water 30 25 20 15 28 45 40 10 15 30 30 25 20 35 30 28 32 15 positions. A typical example of a heavy duty or heavily built granular detergent composition can contain about 17.5% of an active detergent mixture described herein, about 50% sodium tripolyphosphate, about 24% sodium sulfate, and about 8.5% sodium silicate.

It has also been discovered that the synergistic sudsing properties of the novel binary detergent composition described herein can be even further enhanced, by adding to said composition from about 0.1% to about 0.3% by weight of a water hardness salt such as magnesium sulfate, magnesium chloride, calcium sulfate and calcium chloride, or mixtures thereof. Other well-known water hardness salts can also be used such as iron salts and the like. Preferably from about 0.15% to 0.25% by weight of the inorganic salt should be present in the product.

The suds building effect is more pronounced in relatively soft water but it is also effective in so-called medium hard water or hard water. A surprising aspect of this discovery is that the marked improvement in sudsing is not obtained if the equivalent amount of water hardness salts is added to the water solution instead of being present in the detergent product.

It should be understood that the foregoing detailed description and specific examples, while indicating general and preferred embodiments of the present invention, are given by way of illustration only. Various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

What is claimed is:

1. A detergent composition having superior sudsing performance characteristics consisting essentially of a synergistic mixture of Detergent A and Detergent B wherein Detergent A is a mixture of from about 30% to about 70% of Component A, from about 20% to about 70% of Component B and from about 2% to about 15% of Component C, wherein:

(a) said Component A is a mixture of double-bond positional isomers of water-soluble salts of alkene-lsulfonic acids containing from about 12 to about 16 carbon atoms, said mixture of positional isomers including about 10% to about 25% of an alpha-beta unsaturated isomer, about 30% to about 70% of a beta-gamma unsaturated isomer, about 5% to about 25 of a gamma-delta unsaturated isomer, and about 5% to about of a delta-epsilon unsaturated isomer;

(b) said Component B is a mixture 'of water-soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds containing from about 12 to about 16 carbon atoms, the functional units being hydroxy and sulfonate radicals with the sulfonate radical always being on the terminal carbon and the hydroxyl radical being attached to a carbon atom at least two carbon "atoms removed from the terminal carbon atom with at least 90% of the hydroxy radical substitution being in the 3, 4, and 5 positions; and

(c) said Component C is a mixture comprising from 30- 95% water-soluble salts of alkene disulfonate containing from about 12 to about 16 carbon atoms, and from about 5% to about 70% water-soluble salts of hydroxy disulfonates containing from about 12 to about 16 carbon atoms, said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atom, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate radical attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group; and wherein Detergent B is an alkyl glyceryl ether sulfonate having a straight chain alkyl group having from about 10 to about 16 carbon atoms, the cation of said sulfonate being selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, ammonium, sodium, and potassium cations and mixtures thereof,

the ratio of Detergent A to Detergent B being from about 10:1 to about 1:7 by weight.

2. A detergent composition prepared according to claim 1 wherein the ratio of Detergent A to Detergent B is from 6:1 to 1:4 by weight.

' 3. A detergent composition prepared according to claim 1 wherein the alkyl group of Detergent B contains from about 12 to about 16 carbon atoms.

4. A detergent composition prepared according to claim 1 wherein the alkyl gr-oup of Detergent B is derived from coconut oil.

5. A liquid detergent composition consisting essentially of from about 5% to about 50% of the composition described in claim 1, and from about 50% to about 95% water.

6. A liquid detergent composition of claim 5 wherein the detergent composition is present at from about 10% to about 35% by weight of the composition and the water is present at from about 65% to 7. A liquid detergent composition consisting essentially of from about 5% to about 50% of the detergent composition described in claim 1, Water and from about 4% to about 30% of a detergency builder selected from the group consisting of water soluble inorganic alkaline builder salts, organic sequestering agents and mixtures thereof.

8. A liquid detergent composeition of claim 7 wherein the detergency builder is employed at a level of from about 8% to about 25 9. A liquid detergent composition of claim 7 wherein the detergency builder is potassium pyrophosphate.

10. A liquid detergent composition of claim 7 wherein the detergency builder is trisodium ethane-l-hydroxy-l, l-diphosphonate.

11. A liquid detergent composition having synergistic sudsing properties consisting essentially of from about 10% to about 35% of the detergent composition described in claim 1; and from about 8% to about 25 of a detergency builder selected from the group consisting of water soluble inorganic alkaline builder salts, organic sequestering agents and mixtures thereof; from about 2% to about 8% of a hydrotrope selected from the group consisting of sodium, potassium, ethan'olammonium, diethanolammonium, and triethanolammonium salts of benzene sulfonate, xylene sulfonate and toluene sulfonate; from about 5% to about 15% of a solubilizing agent selected from the group consisting of methyl, ethyl and propyl alcohols, with the balance being water.

12. A detergent composition according to claim 1 which also contains from about 0.1% to about 0.3% by weight of a Water hardness salt selected from the group consisting of magnesium sulfate, magnesium chloride, calcium sulfate and calcium chloride.

13. A detergent composition according to claim 12 wherein the water hardness salts is present at a percentage of from about 0.15% to about 0.25% by weight.

References Cited UNITED STATES PATENTS 2,061,617 11/1936 Downing et al. 260513 2,061,618 11/1936 Downing et al 260513 2,061,620 11/1936 Downing et al. 260513. 3,267,040 8/1966 Bright.

(Other references on following page 3,332,374 17 18 OTHER REFERENCES Chem. Ber. 98, 735-742, 1965, Higher Molecular Ali- Alpha 01efine in the Surfactant Industry 1 Amen Oil phatic Sulfonic Acids IV. Sulfonation of Unbranched Al- Chem. Society, November 1963, T. H. Liddicoet, 631- pha'olefins with Puschel and Claus Kaisen 636.

Chem. Ber. 97, No. 10, 2926-33, October 1964, Higher 5 LEON ROSDOL Exammer- Molecular Unsaturated Sulfonic Acids and the Hydroly- S. DARDEN, Examiner. sis of 1,3-A1kanesu1tones, F. Puschel and Claus Kaiser. 

1. A DETERGENT COMPOSITION HAVING SUPERIOR SUDSING PERFORMANCE CHARACTERISTICS CONSISTING ESSENTIALLY OF A SYNERGISTIC MIXTURE OF DETERGENT A AND DETERGENT B WHEREIN DETERGENT A IS A MIXTURE OF FROM ABOUT 30% TO ABOUT 70% OF COMPONENT A, FROM ABOUT 20% TO ABOUT 70% OF COMPONENT B AND FROM ABOUT 2% TO ABOUT 15% OF COMPONENT C, WHEREIN: (A) SAID COMPONENT A IS A MIXTURE OF DOUBLE-BOND POSITIONAL ISOMERS OF WATER-SOLUBLE SALTS OF ALKENE-1SULFONIC ACIDS CONTAINING FROM ABOUT 12 TO ABOUT 16 CARBON ATOMS, SAID MIXTURE OF POSITIONAL ISOMERS INCLUDING ABOUT 10% TO ABOUT 25% OF AN ALPHA-BETA UNSATURATED ISOMER, ABOUT 30% TO ABOUT 70% OF A BETA-GAMMA UNSATURATED ISOMER, ABOUT 5% TO ABOUT 25% OF A GAMMA-DELTA UNSATURATED ISOMER, AND ABOUT 5% TO ABOUT 10% OF A DELTA-EPSILON UNSATURATED ISOMER; (B) SAID COMPONENT B IS A MIXTURE OF WATER-SOLUBLE SALTS OF BIFUNCTIONALLY-SUBSTITUTED SULFUR-CONTAINING SATURATD ALIPHATIC COMPOUNDS CONTAINING FROM ABOUT 12 TO ABOUT 16 CARBON ATOMS, THE FUNCTIONAL UNITS BEING HYDROXY AND SULFONATE RADICALS WITH THE SULFONATE RADICAL ALWAYS BEING ON THE TERMINAL CARBON AND THE HYDROXYL RADICAL BEING ATTACHED TO A CARBON ATOM AT LEAST TWO CARBON ATOMS REMOVED FROM THE TERMINAL CARBON ATOM WITH AT LEAST 90% OF THE HYDROXY RADICAL SUBSTITUTION BEING IN THE 3, 4, AND 5 POSITIONS; AND (C) SAID COMPONENT C IS A MIXTURE COMPRISING FROM 3095% WATER-SOLUBLE SALTS OF ALKENE DISFULONATE CONTAINING FROM ABOUT 12 TO ABOUT 16 CARBON ATOMS, AND FROM ABOUT 5% TO ABOUT 70% WATER-SOLUBLE SALTS OF HYDROXY DISULFONATES CONTAINING FROM ABOUT 12 TO ABOUT 16 CARBON ATOMS, SAID ALKENE DISFULFONATES CONTAINING A SULFONATE GROUP ATTACHED TO A TERMINAL CARBON ATOM AND A SECOND SULFONATE GROUP ATTACHED TO AN INTERNAL CARBON ATOM NOT MORE THAN ABOUT SIX CARBON ATOMS REMOVED FROM SAID TERMINAL CARBON ATOM, THE ALKENE DOUBLE BOND BEING DISTRIBUTED BETWEEN THE TERMINAL CARBON ATOM AND ABOUT THE SEVENTH CARBON ATOM, SAID HYDROXY DISFULFONATES BEING SATURATED ALIPHATIC COMPOUNDS HAVING A SULFONATE RADICAL ATTACHED TO A TERMINAL CARBON, A SECOND SULFONATE GROUP ATTACHED TO AN INTERNAL CARBON ATOM NOT MORE THAN ABOUT SIX CARBON ATOMS REMOVED FROM SAID TERMINAL CARBON ATOM, AND A HYDROXY GROUP ATTACHED TO A CARBON ATOM WHICH IS NOT MORE THAN ABOUT FOUR CARBON ATOMS REMOVED FROM THE SITE OF ATTACHMENT OF SAID SECOND SULFONATE GROUP; AND WHEREIN DETERGENT B IS AN ALKYL GLYCERYL ETHER SULFONATE HAVING A STRAIGHT CHAIN ALKYL GROUP HAVING FROM ABOUT 10 TO ABOUT 16 CARBON ATOMS, THE CATION OF SAID SULFONATE BEING SELECTED FROM THE GROUP CONSISTING OF MONOETHANOLAMINE, DIETHANOLAMINE, TRIETHANOLAMINE, AMMONIUM, SODIUM, AND POTASSIUM CATIONS AND MIXTURES THEREOF, THE RATIO OF DETERGENT A TO DETERGENT B BEING FROM ABOUT 10:1 TO ABOUT 1:7 BY WEIGHT. 